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I’m going to say this as someone that codes very quickly by hand, in a text editor, and knows CSS fluently.
This is a terrible way to design a website.
I’ve done it many times, when design is a low priority and speed is a high priority. What this approach does is lock you into designing based on the needs of the code you’ve written. You lay down basic structure for your page, and get locked into those arbitrary decisions. You become blinded to possibilities that are difficult to style or that you’ve never tried before.
If you want truly cutting edge, innovative web design you do it the right way: you build wire frames, you prototype, you use a raster graphics program while keeping your code in mind, and then you code it. That keeps your mind on the needs of the user and the goals of the site, rather than what content you put in which div.
If you’re doing something fast, cheap, simple or that doesn’t really need to look different than every other website out there, then use this approach. Just don’t use it for serious work.